The present invention relates to a method of formulating pesticide compositions comprising organomodified silylated surfactant compositions that exhibit resistance to hydrolysis over a wide pH range. More particularly the hydrolysis-resistant organomodified silylated surfactants have a resistance to hydrolysis between a pH of about 2 to a pH of about 12.

The topical application of liquid compositions to the surfaces of both animate and inaminate objects to effect a desired change involve the processes of controlling wetting, spreading, foaming, detergency, and the like. When used in aqueous solutions to improve the delivery of active ingredients to the surface being treated, trisiloxane-type compounds have been found to be useful in enabling the control of these processes to achieve the desired effect. However, the trisiloxane compounds may only be used in a narrow pH range, ranging from a slightly acidic pH of 6 to a very mildly basic pH of 7.5. Outside this narrow pH range, the trisiloxane compounds are not stable to hydrolysis, undergoing rapid decomposition.

The present invention provides for a method of formulating a pesticide composition comprising utilizing an organomodified silylated surfactant compound or compositions thereof useful as a surfactant having the general formula:

        (R¹)(R²)(R³)Si -R⁴- Si(R⁵)(R⁶)(R⁷)

wherein
R¹, R², R³ R⁵, and R⁶ are each independently selected from the group consisting of 1 to 6 carbon atom monovalent hydrocarbon radicals, and a hydrocarbon group of 7 to 10 carbons containing an aryl group;
R⁴ is a hydrocarbon group of 1 to 3 carbons.
R⁷ is an alkyleneoxide group of the general formula: R⁸(C₂H₄O)_d(C₃H₆O)_e(C₄H₈O)_fR⁹
where R⁸ is a divalent linear or branched hydrocarbon radical having the structure:

        -CH₂-CH(R¹⁰)(R¹¹)_gO-

where R¹⁰ is H or methyl; R¹¹ is a divalent alkyl radical of 1 to 6 carbons where the subscript g may be 0 or 1;
R⁹ is selected from the group consisting of H, monovalent hydrocarbon radicals of 1 to 6 carbon atoms and acetyl, subject to the limitation that the subscripts d, e and f are zero or positive and satisfy the following relationships: $$\mathrm{2}\mathrm{\le }\mathrm{d}\mathrm{+}\mathrm{e}\mathrm{+}\mathrm{f}\mathrm{\le }\mathrm{20}\mathrm{with\; d}\mathrm{\ge }\mathrm{2.}$$

As used herein, integer values of stoichiometric subscripts refer to molecular species and non-integer values of stoichiometric subscripts refer to a mixture of molecular species on a molecular weight average basis, a number average basis or a mole fraction basis.

The present invention provides for an organomodified silylated surfactant compound or compositions thereof useful as a surfactant having the general formula:

        (R¹)(R²)(R³)Si-R⁴-Si(R⁵)(R⁶)(R⁷)

wherein
R¹, R², R³, R⁵, and R⁶ are each independently selected from the group consisting of 1 to 6 carbon atom monovalent hydrocarbon radicals, and a monovalent hydrocarbon group of 7 to 10 carbon atoms containing an aryl group;
R⁴ is a hydrocarbon group of 1 to 3 carbons;
R⁷ is an alkyleneoxide group of the general formula: R⁸(C₂H₄O)_d(C₃H₆O)_e(C₄H₈O)_fR⁹
where R⁸ is a divalent linear or branched hydrocarbon radical having the structure:

        -CH₂-CH(R¹⁰)(R¹¹)_gO-

where R¹⁰ is H or methyl; R¹¹ is a divalent alkyl radical of 1 to 6 carbons where the subscript g may be 0 or 1;
R⁹ is selected from the group consisting of H, monovalent hydrocarbon radicals of 1 to 6 carbon atoms and acetyl subject to the limitation that the subscripts d, e and f are zero or positive and satisfy the following relationships: $$\mathrm{2}\mathrm{\le }\mathrm{d}\mathrm{+}\mathrm{e}\mathrm{+}\mathrm{f}\mathrm{\le }\mathrm{20}\mathrm{with\; d}\mathrm{\ge }\mathrm{2.}$$

One preferred embodiment of the organomodified silylated surfactant is where R¹, R², R³, R⁵, and R⁶ are each independently selected from the group consisting of 1 to 6 monovalent hydrocarbon radicals, aryl, and a hydrocarbon group of 7 to 10 carbons containing or substituted with an aryl group; preferably a hydrocarbon group of 7 to 8 carbons containing an aryl group and more preferably a hydrocarbon group of 7 carbons containing an aryl group;
R⁴ is a hydrocarbon group of 1 to 3 carbons;
R⁷ is an alkyleneoxide group of the general formula:

        R⁸(C₂H₄O)_d(C₃H₆O)_e(C4H₈O)_fR⁹

where R⁸ is a divalent linear or branched hydrocarbon radical having the structure:

        -CH₂-(R¹⁰)(R¹¹)_gO-

R¹⁰ is H or methyl; R¹¹ is a divalent alkyl radical of 1 to 6 carbon atoms, more preferably 1 to 2 carbon atoms, where the subscript g may be 0 or 1;
R⁹ is selected from the group consisting of H, monovalent hydrocarbon radicals of 1 to 6 carbon atoms and acetyl; more preferably H or methyl, where R⁷ is subject to the limitation that the subscripts d, e and f are zero or positive and satisfy the following relationships:
2 ≤ d + e + f ≤ 20 with d ≥ 2; with d preferably ranging from 3 to 20, and more preferably from 5 to 8; with e preferably anging from 0 to 10; and more preferably 0 to 5; with f preferably ranging from 0 to 8, and more preferably from 0 to 4. 4.

Another preferred embodiment of the organomodified silylated surfactant is where R¹, R², R³, R⁵, and R⁶ are each methyl; R⁴ is a hydrocarbon group of 1 to 3 carbon atoms; R¹⁰ is H; R¹¹ is methyl, where the subscript g is 1. R⁹ is H or methyl. Subscripts d, e and f are zero or positive and satisfy the following relationships:

2 ≤ d + e + f ≤ 17 with d ≥ 2; preferably d ranges from 3 to 9, and more preferably from 5 to 8; preferably e ranges from 0 to 5; and more preferably 0 to 3; preferably f is 0 to 2.

Yet another preferred embodiment of the organomodified silylated surfactant is where R¹, R², R³, R⁵, and R⁶ are each methyl; R⁴ is a hydrocarbon group of 1 or 2 carbon atoms; R¹⁰ is H; R¹¹ is methyl, where the subscript g is 1; the subscript d ranges from 6 to 8, both e and f are 0.

One method of producing the composition of the present invention is to react a molecule of the following formula:

        (R¹)(R²)(R³)Si -R⁴-Si(R⁵)(R⁶)(R¹²)

where R¹² is H, wherein the definitions and relationships are later defined and consistent with those defined above, under hydrosilylation conditions, with an olefinically modified polyalkyleneoxide, such as allyloxypolyethyleneglycol, or methallyloxypolyalkyleneoxide, which are incorporated here as examples, and not set forth to limit other possible olefinically modified alkyleneoxide components. As used herein the phrase "olefinically modified polyalkyleneoxide" is defined as a molecule possessing one or more alkyleneoxide groups containing one or more, terminal or pendant, carbon-carbon double bonds. The polyether is an olefinically modified polyalkyleneoxide (hereinafter referred to as "polyether") is described by the general formula :

        CH₂=CH(R¹⁰)(R¹¹)_gO(C₂H₄O)_d(C₃H₆O)_e(C₄H₈O)_fR⁹

where
R¹⁰ is H or methyl; R¹¹ is a divalent alkyl radical of 1 to 6 carbons where the subscript g may be 0 or 1; R⁹ is H, a monofunctional hydrocarbon radical of 1 to 6 carbons, or acetyl. When the polyether is composed of mixed oxyalkyleneoxide groups (i.e. oxyethylene, oxypropylene and oxybutylene) the units may be blocked, or randomly distributed. Illustrative examples of blocked configurations are: -(oxyethylene)_a(oxypropylene)_b-; -(oxybutylene)_c(oxyethylene)_a-; -(oxypropylene)_b(oxyethylene)_a(oxybutylene)_c-, and the like.

Non-limiting illustrative examples of the olefinically modified polyalkyleneoxide are:

        CH₂=CHCH₂O(CH₂CH₂O)₈H; CH₂=CHCH₂O(CH₂CH₂O)₈CH₃;

        CH₂=CHCH₂O(CH₂CH₂O)₄(CH₂CH(CH₃)O)₅H;

        CH₂=CHO(CH₂CH₂O)₅(CH₂CH(CH₃)O)₅H;

        CH₂=C(CH₃)CH₂O(CH₂CH₂O)₄(CH₂CH(CH₃)O)₅C(=O)CH₃;

        CH₂=CHCH₂O(CH₂CH₂O)₅(CH₂CH(CH₃)O)₂(CH₂CH(CH₂CH₃)O)₂H

Polyether-modified carbosilanes are straightforwardly prepared through the use of a hydrosilylation reaction to graft the olefinically modified (i.e. vinyl, allyl or methallyl) polyalkyleneoxide onto the hydride (SiH) intermediate of the trisiloxane of the present invention.

Precious metal catalysts suitable for making polyether-substituted silanes are also well known in the art and comprise complexes of rhodium, ruthenium, palladium, osmium, iridium, and /or platinum. Many types of platinum catalysts for this SiH-olefin addition reaction are known and such platinum catalysts may be used to generate the compositions of the present invention. The platinum compound can be selected from those having the formula (PtCl₂Olefin) and H(PtCl₃Olefin) as described in U.S. Pat. No. 3,159,601. A further platinum containing material can be a complex of chloroplatinic acid with up to 2 moles per gram of platinum of a member selected from the class consisting of alcohols, ethers, aldehydes and mixtures thereof as described in U.S. Pat. No. 3,220,972. Yet another group of platinum containing materials useful in this present invention is described in U.S. Pat. Nos. 3,715,334; 3,775,452 and 3,814,730 (Karstedt). Additional background concerning the art may be found in J.L. Spier, "Homogeneous Catalysis of Hydrosilation by Transition Metals", in Advances in Organometallic Chemistry, volume 17, pages 407 through 447, F.G.A. Stone and R West editors, published by Academic Press (New York, 1979). Those skilled in the art can easily determine an effective amount of platinum catalyst. Generally an effective amount ranges from about 0.1 to 50 parts per million of the total organomodified silylated surfactant composition.
Pesticide compositions

Many pesticide applications require the addition of an adjuvant to the spray mixture to provide wetting and spreading on foliar surfaces. Often that adjuvant is a surfactant, which can perform a variety of functions, such as increasing spray droplet retention on difficult to wet leaf surfaces, enhance spreading to improve spray coverage, or to provide penetration of the herbicide into the plant cuticle. These adjuvants are provided either as a tank-side additive or used as a component in pesticide formulations.

Typical uses for pesticides include agricultural, horticultural, turf, ornamental, home and garden, veterinary and forestry applications.

The pesticidal compositions formulated according to the present invention also include at least one pesticide, where the organomodified silylated surfactant of the present invention is present at an amount sufficient to deliver between 0.005% and 2% to the final use concentration, either as a concentrate or diluted in a tank mix. Optionally the pesticidal composition may include excipients, cosurfactants, solvents, foam control agents, deposition aids, drift retardants, biologicals, micronutrients, fertilizers and the like. The term pesticide means any compound used to destroy pests, e.g., rodenticides, insecticides, miticides, fungicides, and herbicides. Illustrative examples of pesticides that can be employed include, but are not limited to, growth regulators, photosynthesis inhibitors, pigment inhibitors, mitotic disrupters, lipid biosynthesis inhibitors, cell wall inhibitors, and cell membrane disrupters. The amount of pesticide employed in compositions of the invention varies with the type of pesticide employed. More specific examples of pesticide compounds that can be used with the compositions of the invention are, but not limited to, herbicides and growth regulators, such as phenoxy acetic acids, phenoxy propionic acids, phenoxy butyric acids, benzoic acids, triazines and s-triazines, substituted ureas, uracils, bentazon, desmedipham, methazole, phenmedipham, pyridate, amitrole, clomazone, fluridone, norflurazone, dinitroanilines, isopropalin, oryzalin, pendimethalin, prodiamine, trifluralin, glyphosate, sulfonylureas, imidazolinones, clethodim, diclofop-methyl, fenoxaprop-ethyl, fluazifop-p-butyl, haloxyfop-methyl, quizalofop, sethoxydim, dichlobenil, isoxaben, and bipyridylium compounds.

Fungicide compositions that can be used with the present invention include, but are not limited to, aldimorph, tridemorph, dodemorph, dimethomorph; flusilazol, azaconazole, cyproconazole, epoxiconazole, furconazole, propiconazole, tebuconazole and the like; imazalil, thiophanate, benomyl carbendazim, chlorothialonil, dicloran, trifloxystrobin, fluoxystrobin,dimoxystrobin, azoxystrobin, furcaranil, prochloraz, flusulfamide, famoxadone, captan, maneb, mancozeb, dodicin, dodine, and metalaxyl.

Insecticide, larvacide, miticide and ovacide compounds that can be used with the composition of the present invention, but not limited to, Bacillus thuringiensis, spinosad, abamectin, doramectin, lepimectin, pyrethrins, carbaryl, primicarb, aldicarb, methomyl, amitraz, boric acid, chlordimeform, novaluron, bistrifluron, triflumuron, diflubenzuron, imidacloprid, diazinon, acephate, endosulfan, kelevan, dimethoate, azinphos-ethyl, azinphos-methyl, izoxathion, chlorpyrifos, clofentezine, lambda-cyhalothrin, permethrin, bifenthrin, cypermethrin and the like.

The pesticide may be a liquid or a solid. If a solid, it is preferable that it is soluble in a solvent, or the organomodified silylated surfactant of the present invention, prior to application, and the organomodified silylated surfactant may act as a solvent, or surfactant for such solubility or additional surfactants may perform this function.

Buffers, preservatives and other standard excipients known in the art also may be included in the composition.

Solvents may also be included in compositions of the present invention. These solvents are in a liquid state at room temperature. Examples include water, alcohols, aromatic solvents, oils (i.e. mineral oil, vegetable oil, silicone oil, and so forth), lower alkyl esters of vegetable oils, fatty acids, ketones, glycols, polyethylene glycols, diols, paraffinics, and so forth. Particular solvents would be 2, 2, 4-trimethyl, 1-3-pentane diol and alkoxylated (specially ethoxylated) versions thereof as illustrated in US Patent No. 5,674,832 or N-methyl-pyrrilidone.

Moreover, other cosurfactants, which have short chain hydrophobes that do not interfere with superspreading as described in US Patent No. 5,558,806 are herein included by reference.

The cosurfactants useful herein include nonionic, cationic, anionic, amphoteric, zwitterionic, polymeric surfactants, or any mixture thereof. Surfactants are typically hydrocarbon based, silicone based or fluorocarbon based.

Useful surfactants include alkoxylates, especially ethoxylates, containing block copolymers including copolymers of ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof; alkylarylalkoxylates, especially ethoxylates or propoxylates and their derivatives including alkyl phenol ethoxylate; arylarylalkoxylates, especially ethoxylates or propoxylates, and their derivatives; amine alkoxylates, especially amine ethoxylates; fatty acid alkoxylates; fatty alcohol alkoxylates; alkyl sulfonates; alkyl benzene and alkyl naphthalene sulfonates; sulfated fatty alcohols, amines or acid amides; acid esters of sodium isethionate; esters of sodium sulfosuccinate; sulfated or sulfonated fatty acid esters; petroleum sulfonates; N-acyl sarcosinates; alkyl polyglycosides; alkyl ethoxylated amines; and so forth.

Specific examples include alkyl acetylenic diols (SURFONYL- Air Products), pyrrilodone based surfactants (e.g., SURFADONE - LP 100 - ISP), 2-ethyl hexyl sulfate, isodecyl alcohol ethoxylates (e.g., RHODASURF DA 530 - Rhodia), ethylene diamine alkoxylates (TETRONICS - BASF), and ethylene oxide/propylene oxide copolymers (PLURONICS - BASF) and Gemini type surfactants (Rhodia).

Preferred surfactants include ethylene oxide/propylene oxide copolymers (EO/PO); amine ethoxylates; alkyl polyglycosides; oxo-tridecyl alcohol ethoxylates, and so forth.

In a preferred embodiment, the composition formulated according to the present invention further comprises one or more agrochemical ingredients. Suitable agrochemical ingredients include, but not limited to, herbicides, growth regulators, fertilizers, biologicals, plant nutritionals, micronutrients, biocides, paraffinic mineral oil, methylated seed oils (i.e. methylsoyate or methylcanolate), vegetable oils (such as soybean oil and canola oil), water conditioning agents such as Choice^® (Loveland Industries, Greeley, CO) and Quest (Helena Chemical, Collierville, TN), modified clays such as Surround^® (Englehard Corp.,), foam control agents, surfactants, wetting agents, dispersants, emulsifiers, deposition aids, antidrift components, and water.

Suitable compositions are made by combining, in a manner known in the art, such as by mixing, one or more of the above components with the organomodified silylated surfactant of the present invention, either as a tank-mix, or as an "in-can" formulation. The term "tank-mix" means the addition of at least one agrochemical to a spray medium, such as water or oil, at the point of use. The term "in-can" refers to a formulation or concentrate containing at least one agrochemical component The "in-can" formulation may then diluted to use concentration at the point of use, typically in a tank-mix, or it may be used undiluted.

The hydride intermediates for the organomodified silylated surfactant compositions of the present invention, as well as comparative compositions were prepared as described in the following examples.

The Grignard reagent of trimethylchloromethylsilane (TMCMS) was prepared by reaction of 12.3 g (0.1 mol) TMCMS and 2.88 g (0.12 mol) magnesium chips in THF (50 mL). The Grignard reagent was then added dropwise into 9.46 g (0.1 mol) dimethylchlorosilane (DMCS), which dissolved in THF (50 mL). The mixture was stirred at room temperature overnight and quenched with 20 mL HCl-acidified water, and then extracted with diethylether (100 mL). The organic layer was washed with distilled water three times and dried with anhydrous sodium sulfate. The mixture was purified by distillation at 118-119 °C to yield 13.0 g (89%) (trimethylsilylmethyl)dimethylsilane product as a clear, colorless fluid.

10g (0.1 mol) trimethylvinylsilane (TMVS), 9.46g (0.1 mol) dimethylchlorosilane (DMCS) and 10 µl platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (0.1 M in xylene) were placed into a 100 mL three-necked round bottom flask equipped with N₂ inlet and reflux condenser. The mixture was stirred at room temperature for 30 min and heated to 70 °C for 2h. The reaction was monitored by ¹H NMR. After cooling down to room temperature, 50 mL of THF was introduced and the solution was cooled to -80 °C. 1.00g LiAlH₄ was added to the solution and stirred until the mixture warmed up to room temperature. The mixture was further stirred at room temperature overnight 10 mL of acidified water was added to quench the reaction, and the organic layer was separated, washed with water three times and dried over anhydrous sodium sulfate. The mixture was purified by distillation, and 12.7 g (yield 79.2%) product was collected at b.p. 140-141 °C as a clear colorless fluid.

11.4g (0.1 mol) trimethylallylsilane, 9.5g (0.1 mol) dimethylchlorosilane (DMCS) and 10 µl platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (0.1 M in xylene) were placed into a 100 mL three-necked round bottom flask equipped with N₂ inlet and condenser. The mixture was stirred at room temperature for 30 min and heated to 70 °C for 2h. The reaction was monitored by ¹H NMR. After cooling down to room temperature, 50 mL of THF was introduced and the solution was cooled to -80 °C 1.00g LiAlH₄ was added to the solution and stirred until the mixture warmed up to room temperature. The mixture was further stirred at room temperature overnight 10 mL of acidified water was added to quench the reaction, and the organic layer was separated, washed with water three times and dried over anhydrous sodium sulfate. The mixture was purified by vacuum distillation, and 12.3 g (yield 70.7%) product was collected at b.p. 60-61°C 133-267 Pa (1-2 mmHg) as a clear colorless fluid.

The hydride intermediates of Examples 1-3 were further modified with various allylpolyalkyleneoxides to yield the organomodified silylated surfactant compositions of the present invention (Table 1), as well as comparative trisiloxane surfactants (From Table 2).

The organomodified silylated surfactant compositions of the present invention were prepared by conventional methods of platinum-mediated hydrosilylation, as described in Bailey, U.S. Patent 3,299,112.

Table 1 provides a description of the compositions of the present invention. These compositions are described by the general structure:

        (CH₃)₃Si(CH₂)_mSi(CH₃)₂(CH₂CH₂CH₂O(CH₂CH₂O)_nR⁹),

wherein m, n and R⁹ are described in Table 1. LD. m n R 1 1 7.5 CH₃ 2 2 7.5 CH₃ 3 3 7.5 CH₃ 4 1 7.5 H 5 2 7.5 H 6 1 4 H 7 2 4 H 8 1 11 H 9 2 11 H Table 2 provides a description of the comparative trisiloxane and organosilicone polyether based surfactants of the general structure:

        MD_XD"_Y M

where M = (CH₃)₃SiO_0.5; D = O Si(CH₃)₂; and
D" = OSi(CH₃)CH₂CH₂CH₂O-(CH₂CH₂O)_aR¹³ Polyether Group I.D. X Y a R¹³ A 0 1 7.5 CH₃ B 0 1 7.5 H C 20 3 7.5 CH₃

Additionally, comparative sample OPE (Octylphenolethoxylate, containing 10 polyoxyethylene units) is a non-silicone organic surfactant This product is available as Triton^® X-100 from Dow Chemical Company, Midland, ML

This example demonstrates the ability of the organomodified silylated surfactant compositions of the present invention to reduce aqueous surface tension, thereby showing utility as surfactants. Surface tension was measured using a Kruss surface tensiometer, with a sand blasted platinum blade as the sensor. Solutions of the various components were prepared at 0.1 wt% in 0.005M NaCl water (deionized), as an equilibrium aid.

Table 3 shows that solutions of these unique compositions provide a significant reduction in surface tension relative to the conventional surfactant

The compositions of the present invention also provide spreading properties similar to the comparative trisiloxane surfactants (A, B). Additionally, organomodified silylated surfactants of the present invention provide improved spreading relative to the conventional silicone polyether (C) and conventional organic surfactant product OPE.

Spreading was determined by applying a 10 µL droplet, of surfactant solution to polystyrene Petri dishes (Fisher Scientific) and measuring the spread diameter (mm) after 30 seconds, at a relative humidity between 50 and 70% (at 22 to 25°C). The solution was applied with an automatic pipette to provide droplets of reproducible volume. Deionized water that was further purified with a Millipore filtration system was used to prepare the surfactant solutions. Surface Tension $$\frac{\mathrm{Spread\; Diameter}\left(\mathrm{mm}\right)}{\mathrm{Weight}\%\mathrm{Surfactant}}$$ LD. mN/m 0.05% 0.1% 0.3% 0.5% 1 24.2 24 41 43 45 2 24.6 27 44 44 45 3 23.8 28 44 44 39 4 24.4 23 36 36 22 5 23.6 27 44 40 33 6 22.5 40 45 53 47 7 22.7 30 42 48 49 8 27.7 nd 7 nd 7 9 26.7 nd 7 nd 7 A 20.9 34 53 51 25 B 20.6 37 53 50 35 C 23.6 nd nd nd 6 OPE 31.8 nd 9 nd 10

Hydrolytic stability was determined for representative compositions used in the present invention using HPLC. Solutions of the various compositions were prepared at 0.5 wt% over a pH range from pH 2 to pH 12, and monitored by HPLC for decomposition as a function of time.

The samples were analyzed by a reverse-phase chromatographic technique using the experimental conditions listed in Table 4. Time (min.) % Methanol % Water % Isopropanol 0.0 70 30 0 15.0 100 0 0 20.0 50 0 50 20.1 70 30 0 25.0 70 30 0

Detector:

ELSD/ LTA (Evaporative Light Scattering with Low Temperature Adapter

Conditions:

30°C, 1.95 SLPM N₂

Column:

Phenomenex LUNA C18 end cap, 5 micron, 75x4.6 mm

Flow Rate:

1.0 mL/min.

Inj. Volume:

10 microlitres

Sample:

0.050 g/mL in methanol

Tables 5-7 demonstrate that the compositions of the present invention provide improved resistance to hydrolytic decomposition relative to the standard comparative siloxane-based surfactant Siloxane A, under similar pH conditions.

Comparative siloxane A shows rapid hydrolysis at ≤ pH 5 and > pH 9, while the organomodified silylated surfactants of the present invention demonstrate a higher resistance to hydrolysis under the same conditions. Stability: % Silylated Surfactant Remaining LD. Time pH2 pH4 pH 5 pH7 pH9 pH 10 pH 12 1 24h nd 100 100 100 100 100 nd 1 wk 100 100 100 100 100 100 77 2wk nd 100 100 100 100 100 nd 3 wk 100 nd Nd nd nd nd 73 4 wk nd 100 100 100 100 100 nd 7 wk 89 100 100 100 100 100 76 12 wk 95 100 100 100 100 100 76 19 wk 95 100 100 100 100 100 72 30 wk 73 100 100 100 100 100 74 Stability: % Silylated Surfactant Remaining LD. Time pH2 pH4 pH 5 pH7 pH9 pH 10 pH 12 2. 24h nd 100 100 100 100 100 nd 1 wk 100 100 100 100 100 100 77 2wk nd 100 100 100 100 100 nd 3wk 100 nd nd nd nd nd 77 4wk nd 100 100 100 100 100 nd 7wk 100 100 100 100 100 100 74 12 wk 86 100 100 100 100 100 74 19 wk 79 87 100 100 100 100 77 30 wk 73 79 90 100 94 97 75 Stability: % Siloxane Surfactant Remaining LD. Time pH4 pH 5 pH7 pH 9 pH 10 A 24h 50 93 100 95 75 48h 22 85 100 88 52 1 wk 0 58 100 72 12

Unlike traditional siloxane based surfactants, which are subject to rapid hydrolysis under acidic and basic conditions (≤pH 5 and ≥ pH 9), the organomodified silylated surfactants of the present invention provide increased resistance to hydrolysis relative to traditional trisiloxane alkoxylates (Comparative Example A). An artifact of hydrolysis is observed as a reduction in spreading properties over time. Therefore, solutions of the organomodified silylated surfactants of the present invention, as well as comparative surfactants, were prepared at desired use levels and pH. Spreading was determined as a function of time to illustrate resistance to hydrolysis.

Table 8 is an illustrative example of a traditional organomodified trisiloxane ethoxylate surfactant, which exhibits decreased spreading performance with time as a function of hydrolytic decomposition over a pH range from pH 3 to pH 10. Here a 0.4 wt% solution of product A was prepared at pH 3, 4, 5 and 10. Spreading was determined by applying a 10 µL droplet of surfactant solution to polyacetate film (USI, "Crystal Clear Write on Film") and measuring the spread diameter (mm) after 30 seconds, at a relative humidity between 50 and 70% (at 22 to 25°C). The solution was applied witch an automatic pipette to provide droplets of reproducible volume. Deionized water that was further purified with a Millipore filtration system was used to prepare the surfactant solutions. Spread Diameter (mm) Time Product pH 3 pH 4 pH 5 pH 10 0h A 34 28 29 27 1h A 39 37 27 33 2h A 36 30 33 33 4h A 41 28 28 29 6h A 16 27 27 28 8h A 12 31 29 27 24h A 12 32 25 25 48h A 10 41 25 33 5 days A 7 30 26 36 7 days A 6 17 28 25 14 days A 7 7 37 15

Table 9 is an illustrative example of an organomodified silylated surfactant of the present invention, where product No. 2, a superspreader, has improved resistance to hydrolysis, over a pH range from pH 3 to pH 10 relative to a traditional trisiloxane ethoxylate surfactant (Product A). As mentioned above, resistance to hydrolysis was observed by monitoring the spreading properties over time. Here a 0.1 wt% solution was prepared at pH 3, 4, 5 and 10. Spreading was determined by applying a 10 µL droplet, of surfactant solution to polystyrene Petri dishes (Fisher Scientific) and measuring the spread diameter (mm) after 30 seconds, at a relative humidity between 50 and 70% (at 22 to 25°C). The solution was applied with an automatic pipette to provide droplets of reproducible volume. Deionized water that was further purified with a Millipore filtration system was used to prepare the surfactant solutions. Spread Diameter (mm) Time Product pH 3 pH 4 pH 5 pH 10 0h 2 39 39 41 27 24h 2 37 38 37 35 48h 2 39 39 36 38 72h 2 39 38 39 35 1 week 2 38 39 40 36 2 weeks 2 39 37 39 39 1 month 2 40 39 40 39 2 months 2 43 41 41 41 3 months 2 39 40 37 45 6 months 2 43 40 44 41 12 months 2 45 38 42 41

The impact of other ingredients on spreading was determined by blending the organomodified silylated surfactant of the present invention, with a conventional organic based co-surfactant. The co-surfactants are described in Table 10.

Blends were prepared as physical mixtures where the weight fraction of the silylated surfactant is represented by α (alpha), indicating that the co-surfactant makes up the balance of the blend ratio. For example when α = 0 this indicates that the composition contains 0% of the silylated surfactant component and 100% co-surfactant, while an α =1.0 indicates the composition contains 100% silylated surfactant, and no (0%) co-surfactant. Mixtures of the two components are represented by the weight fraction α, where α ranges as follows: 0 ≤ α ≤1.0. By example when α = 0.25 this indicates the surfactant mixture is composed of 25% silylated surfactant and 75% co-surfactant. These blends are then diluted in water to the desired concentration for spreading evaluation.

Spreading was determined as described in Example 5, at 0.1wt% total surfactant

The silylated surfactant alone at relative concentrations (i.e. α = 0.75 is equivalent to 0.075% of this surfactant in water) was used as a baseline for spread performance, since the major contributor to spreading comes from the silylated surfactant. The maximum spreading provided by the co-surfactant at 0.1%. (α = 0). Synergy is demonstrated when the blend of silylated surfactant and co-surfactant exceeds the spreading of the co-surfactant (α = 0) and the silylated surfactant at the relative α value.

Table 11 demonstrates that representative examples of the co-surfactants of the present invention provide favorable spreading results, and in some cases provide an unexpected synergistic enhancement, where the spread diameter of the mixture exceeds that of the individual components. ID Description PAO-20 Polyoxyethylene/polyoxypropylene copolymer (20% EO) IDA-6 Isodecyl alcohol ethoxylate (5-6 EO) Oxo-TDA-5 Oxo-tridecyl alcohol ethoxylate (5 EO) APG C_8-10 Alkylpolyglucoside Wt Fraction (α) Silylated Surfactant Spread diameter (mm) Run Silylated Surfactan 0 0.25 0.50 0.75 1.0 Co-surfactant 1 2 6 21 32 40 44 PAO-20 2 2 8 26 35 40 44 IDA-6 3 2 24 41 43 45 44 Oxo-TDA-5 4 2 7 21 35 38 44 APG 5 2 NA 13 26 34 44 None^a a. Silylated Surfactant 2 alone at relative concentration (i.e.α = 0.25 is 0.025% product 2).

The foregoing examples are merely illustrative of the invention, serving to illustrate only some of the features of the present invention. Accordingly it is the Applicants' intention that the appended claims are not to be limited by the choice of examples utilized to illustrate features of the present invention. As used in the claims, the word "comprises" and its grammatical variants logically also subtend and include phrases of varying and differing extent such as for example, but not limited thereto, "consisting essentially of" and "consisting of." Where necessary, ranges have been supplied, those ranges are inclusive of all sub-ranges there between. Such ranges may be viewed as a Markush group or groups consisting of differing pairwise numerical limitations which group or groups is or are fully defined by its lower and upper bounds, increasing in a regular fashion numerically from lower bounds to upper bounds.